SU645595A3 - Method of hydraulic treatment of heavy hydrocarbon-type oils - Google Patents

Description

To reduce the content of asphaltenes in the raw material at a temperature of 400-500 ° C, a partial hydrogen pressure of 100-300 atm, a space velocity of 0.2-2.0 i-.

Distinctive features of the method are the use of a catalyst with a definite iroceite of pore size with a diameter of 100-15000 mm and characterized by the ratio of the average diameter of the ion to the average diameter of the particles, as well as before the respectful conditions of the method.

(nm / mm).

-:; .-.

The metals used are one or more metals selected from the group consisting of nickel, cobalt, molybdenum and waiadi. Preferably, the catalyst contains at least one metal selected from the group consisting of nickel, cobalt, and at least one metal selected from the group consisting of molybdenum and vanadium, and, in addition, the atomic the ratio between nickel and / or cobalt on the one hand and molybdeium and / or vanadium on the other was 0.05-3.0. Possible combinations of metals are nickel - vanadium, cobalt - molybdenum and nickel - molybdenum. The number of metals with hydrogenation activity, preferably 0.5 to 10 weight. % better than 2.0-7.5 weight. %., Effective catalysts in the proposed method are containing about 0.5 wt. % nickel and 2 wt. % vanadium, as well as catalysts containing 1 wt. % nickel or cobalt, and 4 wt. % molybdenum. Metals must be present on the carrier in metallic form, or in the form of their oxides or sulfides. Preferred catalysts in which the metals are present on the carrier in the form of their sulfides. The sulfidation of the catalysts of the invention can be reduced by any known method.

Catalysts carriers are oxides of elements of groups II, III or IV of the pediatric table, or mixtures of oxides, for example silica, oxide, aluminum, magnesia, zirconia, aluminosilicate and magnetosilicate. Preferably, alumina or silica is used.

  Carbon black may be used as a carrier, obtained as a by-product with;, incomplete oxidation of hydrocarbons with air, oxygen or a mixture of oxygen with air, in the presence of steam or without py-;

The use of carbon black as a carrier is most effective when using catalysts for treating residual products with high metal content with hydrogen.

Hydroprocessing for demetalized heavy hydrocarbon oils is carried out at 350-150 ° C, pressure 75-175.atm and at a volumetric rate of 2.3-10.

Hydroprocessing to reduce viscosity and asphaltene content is carried out at a temperature of 400-500 ° C, and an arterial pressure of hydrogen of 100-300 atm and a space velocity of 0,, 0.

In the proposed method in. As a heavy hydrocarbon feedstock, oils and bottoms obtained from the distillation of oil under atmospheric or reduced pressures, such as oil residues and after distillation of light fractions, as well as wide and narrow residual fractions are used.

Example 1: Preparation of catalysts.

Catalyst L. The raw material used is alumina obtained by spray-drying, having an average particle diameter of less than 0.05 mm and a specific surface area of 380. 100 g of alumina is applied to a rotating disk and 100 ml of an aqueous solution containing 2.5 are gradually sprayed onto it. l citric acid. The rotating disk, -: provided with a raised edge, 10 cm high, has a diameter of 40 cm, a speed of 40 rpm, is placed at an angle of 45 ° to horizontal maximum. After 15 minutes, parts of the agglomerate were removed from the disk. After drying 120 ° C, a sieve fraction with an average particle diameter of 2.8 mm is separated from the dried material. After calcining for 1 hour at 600 ° C, the particles are impregnated with an aqueous solution containing nickel nitrate and ammonium molybdate. The finally impregnated material is dried at 120 ° G: - and calcined for 1 hour at 500 ° C. The catalyst thus obtained contains 1 weight. including nickel and 4 wt. including molybdenum and 100 weight. including aluminum oxide.

Catalyst B. Catalyst is obtained using the method and catalyst preparation A. 100 ml of an aqueous solution containing 2, 5-nitric acid are used as a granulating liquid.

Catalyst B. Catalyst is prepared according to the method for producing catalyst A. To the starting material, alumina, there are added 2 g of glass powder with an average particle diameter of less than 0.05 mm. After calcination at 600 ° C, another calcination is carried out for 1 hour or 800 ° C. . .-

Catalyst G. Catalyst is prepared according to the procedure for preparing the catalyst L. K

an amount of NH4H2PO4 is added to the impregnating liquid containing nickel and molybdenum, such that the catalyst obtained contains, in addition to 1 wt. including nickel and 4 wt. including molybdenum, 1 wt. including phosphorus per 100 weight. including alumina. The obtained agglomerate particles after being removed from the disk for 1 hour in a rotating drum.

Catalyst D. The catalyst is prepared according to the procedure for preparing the catalyst T. Alumina, prepared by spraying with an average particle diameter of less than 0.01 mm and a specific surface area of 269, is used as the starting material.

Catalyst E. The starting material is carbon black with an average particle diameter of less than 0.01 mm and a specific surface area of 410. Soot was obtained as a by-product in the partial oxidation of hydrocarbons with air. Particles of agglomerate from soot are obtained in the same way

and

as the particles of agglomerate, of alumina, described in the preparation of catalyst A. An aqueous solution of lignosulfonate is used as a granulating liquid. After 15 minutes, the agglomerate particles were removed from the disk. After drying at 120 ° C, a sieve fraction with an average particle diameter of 2.3 mm is isolated from the dry material. After an hour of calcination in a stream of nitrogen at 700 ° C, the particles are impregnated with an aqueous solution containing nigkel nitrate and vanadium oxalate. The catalyst is present at 120 ° C and calcined for 1 hour at 500 ° C in a stream of nitrogen. Semi

The catalyst contains 0.5 wt. including nickel and 2 wt. h. vanadi on 10 weight. h. soot.

Catalyst G-Catalyst according to the method of preparation of catalyst A. Alumina obtained as an initial material, having an average particle diameter of less than 0.05 mm and a specific surface area of 98, is used as the starting material. ; .

Table I

Properties obtained

catalysts are given in table. ,one.

From the catalysts listed in table. I, catalysts A – E have P: d 15, Y 50%, /0,2 ml1g and specific surface area 150. They are obtained by the method of agglomeration of a material with a specific surface area of 200. Catalyst G is given for comparison, it has a specific surface area of 150 mHg and is obtained by an agglomeration method using a starting material with a specific surface area of 200.

When comparing crush resistance and catalyst density, it can be seen that the use of dilute nitric acid as a granulating fluid instead of an aqueous solution of citric acid (catalysts A B, inclusion of glass powder in the starting material, combined with calcination at a temperature above the softening point of glass (catalysts A and B), the application of the post-rotation of the particles of the agglomerate, after they have reached the desired size on the rotating disk (catalysts A and D) leads to improvements and characteristics.

Example 2. The atmospheric distillation bottoms residue of Middle Eastern crude oil containing 62 ppm of vanadium and nickel is subjected to catalytic hydrodemethylization at various volumetric rates using four tons of the analyzer, given in Table. one; raw materials and hydrogen are passed from top to bottom through a cylindrical vertically positioned fixed bed of catalyst at a temperature of 420 ° C, a pressure of 150 bar and a gas release rate of 250 liters of raw materials. The catalysts are used in the form of their sulfides. The results are given in table. 2

T a 5 l n c 2 Catalysts Indicators Volume velocity, h Removal of V H-Ni (wt.%) After passing 5 tons of raw material / kg of catalyst Experiments for catalysts D, E, E illustrate the proposed method for catalyst G included for comparison. Catalysts D and D (having a specific surface area of 150 and obtained from a material with a specific surface area of 200) methods to remove 49 and 50 weight. % V + Ni, respectively, after passing 5 g of feedstock / kg of catalyst with a bulk velocity of 4.6, while catalyst W (with a specific surface area of 150, obtained from a material with a specific surface area of 200) is able to remove only 39 wt. % V + Ni after processing the same amount of feed material per 1 kg of catalyst at a lower space velocity of 2.0 hours. Example 3. Catalysts 3, I, K are obtained according to the method for preparing catalyst L in example 1. As starting material materials use alumina with

specific surface area 410, 290 n 260, respectively. The properties of the catalysts are given in table. 3

Table 3 The demetallization of the feedstock is carried out under the conditions of example 2 using the catalyst G - The activity of the catalysts is 38.35 and 36 wt. % (removable metals), respectively. 1 analyzer 3 has V less than 50% and P: d less than 16. Catalyst I has V above 70%. Catalyst K has a P: d above 300. Example 3. Four catalysts (Table 1) are tested to increase the quality of three heavy hydrocarbon oils, in the form of bottoms at atmospheric distillation of various types of South American crude oil. Residual oils together with hydrogen were passed from top to bottom through a cylindrical, vertically positioned fixed catalyst bed at a temperature of 410 ° C and a gas exit rate of 250 l H2 / kg of starting material. Catalysts are used in the form of their sulfides. The quality of the feedstock, the conditions of the method and the results of the experiments are given in Table. 4 and 5.

Table 5